Metal-loaded molecular sieves



United States Patent 3,013,984 METAL-LOADED MOLECULAR SIEV'ES Donald W. Breck, Tonawanda, N.Y.,'assignor to Union Carbide Corporation, a corporation of New York No Drawing. Filed Sept. 24, 1958, Ser. No. 762,954

12 Claims. (Cl. 252-455) has been found to depend, to a considerable degree, on

the form in which the metal is present in the-reaction zone.

It is an object of this invention to provide a process for introducing elemental zinc and/or zinc oxide into the internal adsorption area of zeolitic molecular sieves.

It is another object of the invention to provide a zincloaded zeolitic molecular sieve which is a superior catalyst, scavenger and getter having a higher specific surface of metal for chemisorption and having a corresponding higher surface activity.

Other objects will be apparent from the disclosure and appended claims.

The process which satisfies the objects of the present invention comprises intimately contacting, in an inert atmosphere, an activated zeolitic molecular sieve with a vapor of zinc metal whereby at least a substantial quantity of the metal vapor is adsorbed by the molecular sieve, and cooling said metal-containing zeolitic molecular sieve in an inert atmosphere, The product so obtained contains the zinc metal in a form having ahigh specific surface which is suitable for chemisorption and catalysis, scavenging, and gettering. Exposure of this material to an oxidizing atmosphere. at elevated temperatures will convert the contained zinc metal tozinc oxide.

zeolitic molecular sieves, both. natural and synthetic, are metal-aluminosilicates. The crystalline structure of these materials is such that arelatively large adsorption area is present inside each crystal. Access to this area subsequent may be had by way of openings, or pores, in the crystal.

Molecules are selectively adsorbed by molecular sieves on the basis of their size and polarity; among other things.

Zeolitic molecular sieves consist basically of three-dimensional frameworks of $0., and A104 t'et'rahedra. The tetrahedra. are cross-linked by the sharing of oxygen atoms. aluminum is balanced by the inclusion in the crystal of a cation, for example metal'ions, ammonium ions, amine complexes, or hydrogen ions. The space between the tetrahedra may be occupied by water or other adsorbate molecules.

The zeolites may be activated by driving off substantially all of the water of hydration. The space remaining in thecrystal's after'activ'ation is available for adsorption of adsorbate molecules Any of this space not occupied by the adsorbed zinc metal atomswill be available for adsorption ofmoleculesliaving a size, shape, and energy which permits entry of the. adsorbate molecules into the pores of the molecular sieves.

The zeolitic molecular sieves to be useful in the present invention, must be capable of adsorbingoxygen molecules at the normal boiling point of oxygen. Included among these are the preferred natural zeolitic molecular sieves, chab'azite, faujasite, erionite, morde'nite, gmelinite, and the calcium form of an'alcite, and the preferred synthetic zeolitic molecular sieves, zeolite A, D, L, R, S, T, X' and Y. The natural materials are adequately described in the chemical art. The characteristics of the synthetic The electrovalence of the tetrahedra containing "ice materials and processes for making-them are provided below.

The general formula for zeolite X, expressed in terms of mol fractions of oxides, is as follows:

' In the formula 'M represents a cation, for example hydrogen or a metal, and n its valence. The zeolite is activated or made capable of adsorbing certain molecules by the removal of water from the crystal as by heating. Thus the actual number of mols of water present in the crystal will depend upon the degree of dehydration or activation of the crystal. Heating to temperatures of about 350 C. has been found suflicient to remove substantially'allof the adsorbed water.

The cation represented in the formula above by the letter M can be changed by conventional ion-exchange techniques. The sodium form of the zeolite, designated sodium zeolite X, is the most convenient to manufacture. For this reason the other forms of zeolite X are usually obtained by the modification of sodium zeolite X.

The typical formula for sodium zeolite X is The major lines in the X-ray diffraction pattern of zeolite X are set forth in Table A below:

In obtaining the X-ray difiraction powder patterns, standard techniques were employed. The radiation was the K00 doublet of copper, and a Geiger counter spectrometer with a strip chart pen recorder was used. The

peak heights, 1, and the positions as a function of 20', where 0 is the Bragg angle, were read from the spectrometer charge. Fromthese, the relative intensities,

where I is the intensity of the strongest line or peak, and d (obs), the interplanar spacing in A., corresponding to the recorded lines were calculated. The X-ray patterns indicate a cubic unit cell of dimensions between 24.5 A. and 25.5 A.

To make sodium zeolite X, reactants are mixed in aqueous solution and held at about C. until the crystals of zeolite X are formed. Preferably the reactants should' be such that in the solution the following ratios prevail:

Sim/A1 0 s-s Na O/SiO 1.2-1.5 mo/Na o 35-60 The general formula for zeolite A, expressed in terms of mol fractions of oxides is as follows:

- hydration or activation of the crystal.

As in the case of zeolite X, the metal represented in the formula by the letter M can be changed by conventional ion-exchange techniques. For purposes of convenience the sodium form of zeolite A, designated sodium When an aqueous colloidal silica sol employed as the major source of silica, zeolite Y may be prepared by preparing an aqueous sodium aluminosilicate mixture having a composition; expressed in terms of oxide-molezeolite A, is synthesized and other forms obtained by the ratios, which falls within one of the following ranges: modification of the sodium zeolite A.

A typical formula for-sodium zeolite A is Range 1 Range 2 Range 3 0.99Na O:l.0Al O :1.85SiO :5.1H,0' The m j r li in the y fi fi n p t rn of Elsi/5333:: 1%t%t8 ith?) ith; zeolite A are set forth in Table below: HO/N 25 20 to 60 20 m 60 TABLE B maintaining the mixture at a temperature of about 100 4 Value of Rcfleetlon in A 100 III. g gfi fi figfi and separaung the crystals 2 9 100 When sodium silicate is employed as the major source 9 69 of silica, zeolite Y may be prepared by preparing an zggf sg 32 aqueous sodium aluminosilicate mixture having a com- 3:53 0:07"' 53 position, expressed in terms of oxide-mole-ratios, falling 3:32 :33? 1g within one of the following ranges: 2.90=|=0.05 55 2.73:.b0.05 12 amines... 22 Range 1 Range 2 Range 3 The same procedures and techniques were employed in 25 retro s10... 1.5 to 1.7 1.9 to 2.1 V obtaining the patterns described in Tables A and B. ';g? 5g :8 3'8 28% 58 To make sodium zeolite A, reactants are mixed in aqueous solution and heated at about 100 C. until the crystalsvof zeolite A are formed. Preferably the reactants maintaining the mixture at a temperature of about 100 should be such that in the solution the following ratios 30 C. until crystals are formed, and separating the crystals prevail: from the mother liquor. Sio Al 0 0543 The composition of zeolite L,.expressed in terms of N b/ i mole ratios of oxides, may be represented as follows: H O/Na 0 -400 35 l.0=l;().lM O:AlzO::6.4:l:0.5SiOzZ1/H;O

The chemical formula for zeolite Y expressed in terms 3 of oxides mole ratios may be written as w ein M designates a etal ts th m n represen e va- 0-9i0r2Na=0iAlaosiwsloziXHio lence of M"; and y may be any value from 0 to wherein W is a value greater than 3 up to about 5 and about fl. X" may be a value up to about 9. The more significant d (A.) values, i.e., interplanar Zeolite Y has a characteristic X-ray powder difiraction spacings, the major lines in Y difiraction P pattern which may be employed to identify zeolite Y. tern of zeolite are'given below in Tab e D- The Xray powder diffraction data are shown in Table C. The values for the interplanar spacing d, are expressed 7 TABLE D in angstrom units. The relative intensity of the lines of 16 1 0 3 317:1:001 the X-ray powder diffraction data are expressed as VS, v 7.52:0.04 3.07:0.01 very strong; S, strong; M, medium; W, weak; and VW, 6.00:0.02 2.91:0.01 very weak. 4.57:0.03 2.65:0.01

TABLE C 4.35:0.04 2.46:0.01 3.91:0.02 2.42:0.01 ma n +m+z= din A. 3.47:0.02 v 2.19:0.01'

substantially all potassium or potassium and sodium ions.

The reactants accordingly employed are readily available and generally water soluble. The exchangeable cations present in the zeolite may then conveniently be replaced by other exchangeable cations.

The potassium or potassium-sodium forms of zeolite L may be prepared by preparing an aqueous metal alu-' mine-silicate mixture having a composition, expressed in terms of mole ratios of oxides falling within the following range: K,o'/ K,o+Na,o From about 0.33 to about 1. rem-m c /SiO From about 0.4 to about 0.5. I SiO,/Al;0;fl.'. From about 15 to about 28. H 0/(K O+ Na O) From about 15 to about 41.

' from-the mother liquor. v

The chemical formula for zeolite D may be written, wherein W is from 3.45 to 3.65, and X, for the fully in terms of oxides, as follows: hydrated form, is about 7.

9i0 2[xNa20. K20] zAlzoamsioz :yHzo Zeol1te R has an X-ray powder d1ffract1on pattern substantially like that shown in Table F. wherem x 1s a value from 0 to 1,, w 1s from about 4.5 to about 4.9, and y, in the fully hydrated form, is about 7. In the preferred form of zeolite D, "x is in the range of from 0.4 to 0.6. TABLE F Zeolite D has an X-ray powder diffraction pattern substanfiauy like that shown in Table X-ray diflraction patterns of zeolite R TABLE E ld=interplanar spacing in A. I/I mmnzrelative intensity] X-ray difiraction patterns of zeolite D [dzinterplanar spacing in A.:I/I max.=relatlve intensity] zeolite R d, A. 100 Zeohte D (III max.)

2- s1 22 0.42 66 5175 10 6.89 67 5.61 26 5.54 15 '5. 10 45 5. 03 62 4. 15 12 4.33 62 4.31 7s 3.98 27 4.13 12 3.89 23 4.02 14 3.60 12 3.92 35 a. 45 3.80 16 3.19 15 3.63 41 2. 94 100 3.48 25 2.69 9 3.34 12 2. 01 3s a. 21 1s 2. 30 16 3.13 12 2.00 22 2.95 100 1.81 29 30 3.89 16 1.73 23 2.80 14 2.71 14 2.66 10 2.02 25 Zeohte D may be prepared as follows: 7 2. 53 22 A sodium-potassium aluminosilicate-water mixture is gig prepared such that the initial composition of the reactant 2.10 14 in terms of oxide-mole-ratios is: 33 ig 1- 2 K O .7

TF-=0.45 to 0.65 i-g; g

N520 t 0.92 Na O+K O 74 =about 28 Zeolite R may be prepared as follows:

1203 A sodium aluminosilicate-water mixture is prepared such that the initial composition of the reactant mixture, H 1 all f -=18 t 45 m terms. of 0x1 e mo e rat1os, f s w1th1n any one o Na2O+K2O the following seven ranges:

I II III IV V VI VII Nam/$101-- 0.20 to 0.40 0.41 to 0.60 0 51 to 0.80 0.s1 to 1.0 0.81 :5 1.0 1 to 1.9 1.2 to 1 4 5101/4110," about 4 3.5 to 6.0 3.5 to 6.5 3 to 4.5 about 30 10 to 25 a'cout 0 H2o/Nd20-- 22 to 60 30 to 00 40 to 80 40 to so to 00 to 30 10 00 The mixture is maintained at a temperature within The miXture is maintained at a temperature within the range of about C. to C. until crystals are 70 the range of about 100 C. to 120 C. until crystals are formed; the crystals are then separated from the mother formed; the crystals are then separated from the mother liquor. liquor.

The chemical formula for zeolite R may be written as: T e chemical formula for zeolite S may be written 0.9 102N330 I A1203 :WSiO :XH O i 75 0.9i0.2Na O :A1 O3 IWSlOz ZXH O TABLE G X-ra y difiraction patterns of synthetic zeolite S [d=interplanar spacing in A. I/I max.=relative intensity] (111 max.)

11. 88 77 7. 73 19 7. 16 100 I 5. 96 9 5. 03 72 4. 50 46 4. 12 79 3. 97 20 3. 44 62 3. 305 13 3. 236 23 2. 973 80 2. 858 47 2. 693 19 2. 603 39 2. 126 ll 2. 089 39 1. 910 12 1. 809 40 1. 722 32 Zeolite S may be prepared by preparing a sodium aluminosilicatewater mixture such that the composition of the reactant mixture, in terms of oxide-mole ratios, falls within the following range when the source of silica is an aqueous colloidal silica sol:

Na O/SiO A1203 6 t H O/Na O 20 to 100 and falls within the following range when the source of silica is sodium silicate:

Na O/ AbQlll'. 0.5 Slog/A1303 About 25 H O/Na O About maintaining the mixture at a temperature in the range of from about 80 C. up to about 120 C., preferably at about 100 C., and at a pressure at least equal to the vapor pressure of water in equilibrium with the mixture of reactants until crystals are formed, and separating the crystals from the mother liquor.

The chemical formula for zeolite T may be written, in terms of mole ratios of oxides, as follows:

wherein x may be any value from about 0.1 to about 0.8, and y may be any value from about 0 to about 8. Zeolite T may be identified and distinguished from other zeolites, and other crystalline substances, by its X-ray powder diffraction pattern. The data which are set forth below in Table H are for a typical example of zeolite T.

TABLE H-Continued Interplanar Relative Bragg Angle, 20 Spacing, Intensity,

Zeolite T may be prepared by preparing an aqueous sodium-potassium aluminosilicate mixture having a composition, expressed in terms of mole ratios of oxides, falling within the following range:

Na O/(Na O+K O)l From about 0.7 to about 0.8. (Na O-l-K OHSiO From about 0.4 to about 0.5 SiO /A1 O About 20 to 28.

H O/(Na- O+K O) About 40 to 42.

To prepare the elemental metal-containing zeolitic molecular sieves by the process of the present invention, it is first necessary to activate the zeolitic molecular sieves, i.e., to drive off substantially all of the contained water. This may be accomplished by heating the zeolitic molecular sieves up to a temperature of about 350 C. in a flowing stream of inert dry gas or in a vacuum. The activated molecular sieve is then ready to receive the zinc metal vapors.

The activated zeolitic molecular sieves and the zinc metal vapors may be brought into contact with each other by mixing molten zinc and the molecular sieves, by vaporizing the zinc in the presence of the molecular and passing the metal vapor-containing gas stream through a bed of the molecular sieves.

In an example of the invention a glass tube, horizontally mounted in a furnace was packed with 12 grams of powdered zinc metal and 25 grams of sodium zeolite X pellets in the rangeof 14 to 30 mesh size. The zinc metal powder and sodium zeolite X were retained in the tube and were separated from each other with plugs of glass wool. The temperature of the furnace was raised to 350 C. and ,held there for 2 hours while a slow stream of helium was passed through the glass tube first through the metal powder and then through the zeolitic molecular sieve to remove any water in the zeolite. The temperature was then raised to 650 C. and held there for 2 hours with the helium flow continuing. Zinc vapor was entrained in the helium stream and passed into and through the zeolite bed. Upon cooling the system in helium the bed was found to be a gray color. When the zeolite was removed to the air it was found to contain 1.2 weight percent of zinc oxide, the zinc having been converted to the oxide upon contact with the air.

Many advantages accrue from the use of zinc-loaded ,zeolitic molecular sieves that are not available with other materials. For example, it is well known that zinc is a good catalyst for the synthesis of methanol. However, by employing a zinc-loaded zeolitic molecular sieve as the catalyst, it is possible to synthesize methanol from a mixture of gases which might interfere with the syn thesis or compete for the catalytic surface except for the fact thatthe molecular sieve-contained zinc is selective to those materials small enoughto pass into the inner sorption area of the molecular sieves without catalyzing the reaction of larger molecules.

Similarly, zinc has been recognized as a good getter for oxygen and other gases. However, the zinc-loaded zeolitic molecular sieves may be employed for selective gettering from a mixed system, without contamination of the system being so treated.

Still another advantage of employing the product of the present invention resides in the manner in which the metal is held in the molecular sieve. Catalysts consisting of zinc metal on a catalyst support usually have the problem that the metal tends to migrate in the catalyst bed with a corresponding tendency for the metal to collect in some areas of the bed leaving other areas metal deficient. This tends to decrease the active metal surface available for catalysis and to give non-uniformity of catalysis through the bed. By incorporating the metal on the inside of the zeolitic molecular sieves, the tendency for the metal to migrate is minimized with a corresponding increase in the efiiciency of catalysis.

By incorporating the zinc in the zeolitic molecular sieves in accordance with the present invention, a suitable means for adding zinc to other chemical systems is provided. By adding the zinc in this form, it is possible to control the reactivity of the metal to a much greater extent than is possible by direct addition of the metal to the same chemical systems.

Still another use for the zinc-loaded zeolitic molecular sieves of the present invention is in the preparation of zinc oxide-loaded molecular sieves by exposure of the zinc-loaded molecular sieves to an oxidizing atmosphere at elevated temperatures. The oxidized product is also a good catalyst for the methanol synthesis.

As used herein the term activation is employed to designate the removal of water from the zeolitic molec ular sieves, i.e., dehydration, and does not refer to catalytic activity. The zeolitic molecular sieves containing the elemental metal and/or metal oxides exhibit catalytic activity.

The product of the present invention has a surface area about four times that expected with most alumina, silica or aluminosilicate supported metals thereby providing a greater surface area available for reaction. Since the external surface of the molecular sieve represents less than 1 percent of the total surface, area it may be seen that there is an extremely large area available for chemisorption and catalysis in the internal portion of, the molecular sieves. Since this region is available only through pores of molecular size it may be seen that selective chemisorption and catalysis may be obtained in a system containing a mixture of molecules some of which are too large to enter the pores whereas others are capable of entering the pores.

Zeolite A is described and claimed in U.S.- Patent No. 2,882,243, issued April 14, 1959, to R. M. Milton.

Zeolite D is described and claimed in U.S. patent application Serial No. 680,383, filed August 26, 1957.

Zeolite L is described and claimed in U.S. patent application Serial No. 711,565, filed January 28, 1958.

Zeolite R is described and claimed in U.S. patent application Serial No. 680,381, filed August 26, 1957.

Zeolite S is described and claimed in U.S. patent application Serial No. 724,843, filed March 31, 1953.

Zeolite T is described and claimed in U.S. patent application Serial No. 733,819, filed May 8, 1958, now U.S. Patent No. 2,950,952.

Zeolite X is described and claimed in U.S. Patent No. 2,882,244 issued April 14, 1959, to R. M. Milton.

Zeolite Y is described and claimed in U.S. patent application Serial No. 728,057, filed April 14, 1958.

The preferred compositions of matter for the present invention whichhave been found to be most satisfactory and useful for catalytic purposes are the metal-loaded zeolites X, Y, and faujasite. I

Erionite is a naturally occurring Zeolite, described originally by Eakle, Am. J. Science (4), 6, 66 (1898). It is most readily identified by its characteristic X-ray powder ditfraction pattern. The d-spacings, in A., and relative intensities thereof, obtained on a well-crystallized specimen are tabulated below.

X-ray powder data, erzomte d-spncing, Relative A. Intensity,

I/IoXlOO What is claimed is:

1. As a new composition of matter a dehydrated rigid 1 region of said crystalline metal aluminosilicate Zeolite.

2. A process for preparing an elemental zinc-loaded zeolitic molecular sieve which comprises dehydrating a rigid three-dimensional crystalline metal aluminosilicate zeoliteof the molecular sieve type capable of adsorbing oxygen internally at the normal boiling point of oxygen whereby substantially all of the water of hydration of said crystalline metal aluminosilicate Zeolite is removed; intimately. contacting, in an inert atmosphere said dehydrated crystalline metal aluminosilicate Zeolite with elemental zinc vapor, the temperature of said vapor being below the temperature of crystal destruction for said crystalline metal aluminosilicate Zeolite, whereby said metal vapor is adsorbed into the inner adsorption region of said dehydrated crystalline metal aluminosilicate Zeolite; and cooling said dehydrated crystalline metal aluminosilicate Zeolite containing said adsorbed metal vapor in an inert atmosphere whereby said adsorbed elemental zinc vapor is retained in the inner adsorption region of said crystalline metal aluminosilicate zeolite.

3. A process for preparing an elemental zinc-containing rigid three-dimensional crystalline metal aluminosilicate zeolite of the molecular sieve type which comprises dehydrating a rigid three-dimensional crystalline metal aluminosilicate zeolite of the molecular sieve type capable of adsorbing oxygen internally at the normal boiling point of oxygen whereby substantially all of the water of hydration of said crystalline metal aluminosilicate zeolite is removed; intimately contacting said dehydrated crystalline metal aluminosilicate zeolite wtih an inert gas containing entrained zinc vapor, said inert gas and said I entrained zinc vapor being at a temperature below the temperature of destruction of said dehydrated crystalline metal aluminosilicate zeolite crystal whereby said zinc vapor is adsorbed into the inner adsorption region of said dehydrated crystalline metal aluminosilicate zeolite; and cooling said dehydrated crystalline metal aluminosilicate zeolite containing said adsorbed zinc vapor whereby elemental zinc is retained in the inner adsorption region of said crystalline metal aluminosilicate zeolite.

4. As a new composition of matter a dehydrated rigid three-dimensional crystalline metal aluminosilicate zeolite of the molecular sieve type chosen from the group consisting of zeolite A, zeolite D, zeolite L, zeolite R, zeolite S, zeolite T, zeolite X, zeolite Y, chabazite, faujasite, mordenite, erionite, gmelinite and the calcium form of analcite containing a material selected from the group consisting of elemental zinc and zinc oxide in the inner adsorption region ofsaid crystalline metal aluminosilicate zeolite.

5. A composition of matter as described in claim 4 wherein the crystalline metal aluminosilicate zeolite is zeolite A.

6. A composition of matter as described in claim 4 wherein the crystalline metal aluminosilicate zeolite is zeolite X.

7. A process for preparing an elemental zinc-loaded rigid three-dimensional crystalline metal aluminosilicate zeolite of the molecular sieve type which comprises dehydrating a rigid three-dimension crystalline metal aluminosilicate zeolite of the molecular sieve type chosen from the group consisting of zeolite A, zeolite D, zeolite L, zeolite R, zeolite S, zeolite T, zeolite X, zeolite Y, chabazite, faujasite, erionite, mordenite, gmelinite and the calcium form of analcite thereby substantially all of the water of hydration of said crystalline metal aluminosilicate zeolite is removed; intimately contacting in an inert atmosphere said dehydrated crystalline metal aluminosilicate zeolite with elemental zinc vapor, the temthe inner adsorption region of said dehydrated crystalline metal aluminosilicate zeolite; and cooling said dehydrated crystalline metal aluminosilicate zeolite containing said adsorbed metal vapor in an inert atmosphere whereby said adsorbed elemental zinc vapor is retained in the inner adsorption region of said crystalline metal aluminosilicate zeolite.

8. A process for preparing an elemental zinc-containing rigid three-dimensional crystalline metal aluminosilicate zeolite of the molecular sieve type which comprises dehydrating a rigid three-dimensional crystalline metal aluminosilicate zeo 'te of the molecular sieve type chosen from the group consisting of zeolite A, zeolite D, zeolite L, zeolite R, zeolite S, zeolite T, zeolite X, zeolite Y, chabazite, faujasite, mordenite, erionite, gmelinite and the calcium form of analcite whereby substantially all of the water of hydration of said crystalline metal aluminosilicate zeolite is removed; intimately contacting said dehy drated crystalline metal aluminosilicate zeolite with an inert gas containing entrained zinc vapor, said inert gas and said entrained zinc vapor being at a temperature below the temperature of destruction of said dehydrated crystalline metal aluminosilicate zeolite crystal, whereby said zinc vapor is adsorbed into the inner adsorption region of said dehydrated crystalline metal aluminosilicate zeolite; and cooling said dehydrated crystalline metal aluminosilicate zeolite containing said adsorbed zinc vapor whereby elemental zinc is retained in the inner adsorption region of said crystalline metal aluminosilicate zeolite. I

9. A process as described in claim 7 wherein the crystalline metal aluminosilicate zeolite is zeolite A.

10. A process as described in claim 7 wherein the crys talline metal aluminosilicate zeolite is zeolite X.

11. A process as described in claim 8 wherein the crystalline metal aluminosilicate zeolite is zeolite A.

12, A process as described in claim 8 wherein the crystalline metal aluminosilicate zeolite is zeolite X.

References Cited in the file of this patent UNITED STATES PATENTS 1,840,450 Iaeger et al. I an. 12, 1932 2,306,610 Barrer Dec. 29, 1942 2,413,134 Barrer Dec. 24, 1946 2,617,712 Bond Nov. 11, 1952 2,859,257 Hess Nov. 4, 1958 2,882,243 Milton Apr. 14, 1959 2,882,244 Milton Apr. 14, 1959 

1. AS A NEW COMPOSITION OF MATTER A DEHYDRATED RIGID THREE-DIMENSIONAL CRYSTALLINE METAL ALUMINOSILICATE ZEOLITE OF THE MOLECULAR SIEVE TYPE CAPABLE OF ADSORBING OXYGEN INTERNALLY AT THE NORMAL BOILING POINT OF OXYGEN CONTAINING A MATERIAL SELECTED FROM THE GROUP CONSISTING OF ELEMENTAL ZINC AND ZINC OXIDE IN THE INNER ADSORPTION REGION OF SAID CRYSTALLINE METAL ALUMINOSILICATE ZEOLITE. 